Chromium complex compounds



pounds which maybe represented by'the prob Patented Sept. 15, 1936 UNITED STATES.

i I. 2,054,490 PATENT OFFICE v No Drawing Applicatiom-Juncifi, 1934, Serial :No. 732,537. .ln GermanyiFebtuary-iz, 1932 'Thepresentinvention relates to new chromium complex compounds of i-amino-l--'hydroxyben-- zene-2-carboxyl1c acid and its nuclear substitution products, more particularly it relates to comable general iormula: a

wherein R stands i fo ra radical or the serie's'i'n whichCOOH stands-in O-position NH: in p-po sitionto m--O-, and 1: stands tor-the:

group I 1 1 iii in which group the Figure B stands rora nondia zotizable organic base, wherein the molecule may besides contain water, 'z'm'd' wherein, the benzene niicleus' may: beariurther-substituents, suchas alkyl, alkoxy, the nitro group, halogen and the sulfonic acid group.

As non-diazotizable'baseswhich may be present in my new complex compounds there may be mentionedfby way it-example primar secondary and tertlaryaliphatic bases and secondary; and

tertiaryaromatic'bs'es,"such asethylenediamine, dibutylamine, piperidine, tributylamine, ethylaniline, dimethylaniline, pyridineano, quino'linel My new chromium 'compiex' compoundsjcom 'taining a non-diazotizable'organic b'ase'in-Whe molecule are obtainable by treatingihe 4-aminol-hydroxy-Z-carboxylic acids or their water soluble salts in water orin'an or'zanimmedium, such as alcohoh or in an aqueous organic medium, such as dilute aqueous. alcohol, with a chromium salt of the kind referred to'aboveand with the addition of a non-diazotizable base. Fayorably the reaction is carried out with the application of heat, for example, by refluxing: however, the reaction may also be carried out at room temperature, for example, by stirring .at .room temperature for a prolonged time, say 'Ior's'everal days.

In carryingqout the' inyention-care is' to'b'e taken-that for'one molecular proportion of'ii amin'o-l hydroxybenzenez-carboxylic acid at least one molecular proportion oit henon-diazo tizablebaseis presentg generally, however, I am working with an excess of the non-diazotizable base.

The quantity of the chromium salt required for producing the new chromium complex com- I OH I: QIQEPX; I (Ham er o I pounds corresponds A molecular equivalent proportion rordzmolecular proportion of the 4- amino1 hydroxy 2-carboxylic :acid. However, it

' should he mentioned that the process can be per-- iormod with-excess chromium selt or with less than the theoreticai quantitnzinztheformer case the excess chromium remaining unconsumed in the reaction mass, .while in the latter case only part of the Aeamino-i-hydroxvbenzene-mcarboxylic acid beingtranstormed into the chromium complex compound. 3

From the reaction mass thenew chromium complex-compounds containing-chromium and thernonediazotizahlo abosmeithermholly or partiallyrseporotoiin-nicnvstailine term or remain insolution. -'r =r,.'ir-. 2 .7

Those. complex do tree from water are in [formed theirialkali mtelisaltsseneraily yellowisb-m brown substances, while those containing watermenorallu areobitained in form of colorless .to -v.io1et 1to weakly brownish substances.

mlmcmyimsentnkncmledze I cannotsay that the/,opnstitinion-ammtod'above of the new complexicompounds is correct; from the analysis of the complex compounds containing waterw i-ardlno-Bhydroxybenzene-Z- mms ic acid 'however, it may be concluded that compound corresponds to the following respectiveib from which the general formula: disclosed ve would result ie-oe =obromiw ow compounds ioqlmloal r-yomb snmduw for the. ioiiowiwz "W1.Qv-WWJrhV KYW boxyiic ncid and, its. amen. substitution products yleid dioz compounds-which can be=coupl d with ,oouplinmcomponentssuitable for promow r-wup s or :14 m c mpounds, meverflis so low that QIBYFDQIZWCQJJPJG withlcomoonents easily couplinz-,,;fl'hus. ,i t.wmvle. t h present it is nqtmossiblanhpll .orrnlydimculuy possible diazo compounds-oi 4-amino-i- WQWKWPMQEQWEWH 80168 w -W- Weoh hWM- acid, w h 2-m- W. Mid-61 mm wider with 2- hydroxynaphthalenewafl-dis dionic.acid. or with 2ehydroxynaphthalened snlfoniq acid.with salicylic acid or with cresotinic-gcid; Nowl haye round that the energy 'of coupling with diazo compounds of 4-amino-1-hydroxybenzene-2-carboxylic acid and its nuclear substitution products is highly increased when diazotizing the complex chromium compounds of the same obtainable in accordance with the present invention which complex compounds can be dii'tzotirlecl in} the usual manner'and coupled with couplinr'components suitable for producing azodyestuffs.

The invention is illustrated by the following' examples, without being limitedthereto; Example 1.--230 grams of 4-amino-1-hydroxybenzene-Z-carboxylic acid are refluxed for about f three hours in 500 cos. of 'water'with 25Qjccsfof pyridine and 250 grams of an aqueous chromium chloride solution of a strengthporrespondingto 2'70 grams of CraOs in one litres During the.re-.

action a brownish-violet chromium-pyridine 7 compound of the 4-amino-1-hydroxybenzene-2- carboxylic. acidyseparates. .When the reaction. is complete, the newcomplex compound is filtered, with suction, washed .with water and dried. It. is a crystalline. substance .ofthe -molecular formula: C24.H3i-Ni-Ol1-'Cr,. and probably has the following constitution:

It can be diazotized in -the-usual manner, forexarnpie, with sodlum'nltrite and hydrochlorieorsulfuric acid, yielding -a reddish-brown crystal-- line diazo compound, easily soluble in water and probably corresponds to the following formula:

- l L- Q 1 It is difflcultly soluble in water; easily'soluble in aqueous soda solutio'rior 'in aqueousf'ammonia. It can be diazotized in the usual manner yielding a reddish-brown crystalline diaz'o compound, which is easily soluble in-water and couples with coupling compogents to form azodyestufls;

Examplei- 0 'gr'amso'f 4-a'mir'io 6 methyl-l hydroxybenzene-2 carboxyllo acid are refluxed for about 3 hoursin-iO ccs. of water with 40 ccs. of pyridine and 21 cos. of an aqueous chromium chloride solution of'a strensthoorrespondini to 270 grams of Orzo: in'one litre. In the course of the reaction a brownish crystalline mass separates. when thercaction incomplete, the comlcx compound formed-is filtered with suction, washed with water and dried. It has properties similar to those of the substance obtainable in accordance with Example 1.

Example 4.35 gra s of 6-sulfo-4-amino-lhydroxybenzene-Z-carboxylic acid are refluxed for about 3 ;hours in 50 ce's.'of water with- 510 ccs. of'triethanolamineand 21-"ccs': of*an aqueous chromium sulfate solution of a. strength corresponding to 290 grams of CrzOa in one litre. .When the reaction is complete, the reaction mixture is allowed to cool, and the complex chromium-triethanol- 6 -sulfo- 4 -amino- 1 -hydroxy- "benzene-2-carb63y1ic acid compound formed is precipitated by saiting out. After filtering and drylng it is.;obtained :as a greenish-grey substance, soluble in water and which can be diazosolution, containins. 27,0 .grarnsot CrzO: in one. Iitre andAQO parts ofan aqueous methylamine solution of 25% strength. After, coolingavioletbrown solution is obtained to which ice is added. The, solution is acidified with acetic acid, whereby a greyish-green precipitate is separated. After filtering with suction itis washed with water and dried on the air. The mcnuumamem ismme- 4 "-amino 1 hydr'oxi'benzene 2 -'-ca'rboitylic acid thus (:.btaineci is a grayish-green powder which can be diazotized with acetic acid and nitrite and which couples with coupling components.

This application is a continuation-in-part of application Ser. No. 653,927, filed January 27, 1933.

'1 As a new product, a'compoundselected from the group consisting of chromium complex compounds of the general formula: 1

whereinB'stands. for a radical o'fxthe benzene series in which COOHQjstands in' 'ortho-positi'on and NH: in para-positlonto and :2: stands ompoundo'fthe'formulai f' -QO J being a crystalline substance. yielding a reddishbrown crystalline diazo compound, easily soluble in water and couplins withcouplin: components to form azodyestufls.

RICHARD BTUBSER. 

